The present study reports the fabrication of free-standing nanomembranes with semiconducting and biodegradable properties. Nanomembranes have been prepared by spin-coating mixtures of a semiconducting polythiophene derivative, poly(3-thiophene methyl acetate), and a biodegradable polyester, poly(tetramethylene succinate). Both the roughness and thickness of the nanomembranes, which ranged from 3 to 20 nm and from 20 to 80 nm, respectively, were precisely controlled through the spin-coater speed and the solvent evaporation properties. Nanomembranes made of conducting polymer/polyester blends, which are able to retain the properties of the individual polymers, are stable in air and in ethanol solution for more than one year, facilitating their manipulation. Enzymatic degradation essays indicated that the ultra-thin films are biodegradable due to the presence of the aliphatic polyester. Interestingly, adhesion and proliferation assays with epithelial cells revealed that the behavior of the blend as cellular matrix is superior to that of the two individual polymers, validating the use of the nanomembranes as bioactive substrates for tissue regeneration.